Polymerized fatty oils and method of preparing same



United States Fatent O POLYMERIZED FATTY EJILS AND METHOD OF PREPARING SAME Max Kantor and Samuel Guy Wilson, Minneapolis, Minn.,

assignors to Cargill, Incorporated, Minneapolis, Minn a corporation of Delaware No Drawing. Application February 9, 1953 Serial No. 336,098

2 Claims. (Cl. 260-407) This invention relates to improvements in a process and the product resulting from polymerizing unsaturated fatty oils with the aid of an active catalyst. In particular it is related to a method of polymerizing drying and semidrying oils at relatively moderate temperatures to produce a final product which is relatively light in color, is of stable viscosity, possesses non-penetrating characteristics, has a high mineral spirits tolerance, and is compatible with odorless mineral spirits and other substances used in protective coatings. The product is produced from unsaturated fatty oils which have been previously blown with air or an oxygen containing gas to form oxygen addition products at the double bonds of the fatty substance and the products so treated are catalytically polyor hydroxy groups.

merized with an active acid catalyst of a class which is peratures causes the polymerization to take eifect in dilfer-' ent ways, frequently joining the molecules by a carbon to carbon linkage. Oils which have been air blown at moderately elevated temperatures have a limited mineral spirits tolerance as well as limited 'drying qualities and their non-penetrating qualities are poor; If the temperature is increased a higher mineral spirits tolerance isobtained, but the oils have different working properties, which are equally undesirable. It is well known that unsaturated oils may be polymerized with certain other ac-- tive catalysts, but frequently such catalysts enter into the reaction and constitute a part of the final product so that the product is subject to further change, or possible reaction with active pigments and might change the color or condition of the coating substance.

One major distinction of the product forming the present invention is in its compatibility with other materials used in coatings, as Well as odorless mineral solvents. The normal mineral spirits which have been used heretofore have been objectionable for use with interior paints because of the irritating odor of certain aromatic components of the solvent. Odorless solvents can be made by removing the aromatic components, but when this is done the solvency power is materially reduced, and in sofar as we areaware, the present product is the only oxidized polymerized oil which is sufiiciently soluble in odorless mineral spirits to be used for coating substances.

Another important distinction is the compatibility of the present product with heat polymerized oils and synthetic resins. In some paint products it is desirable to have a blend of products in the vehicle. While it has been possible heretofore to blend products while warm,

on standing such products become cloudy and eventually Y the charring of the oil.

2,8385% Patented June 10, 1958 separate. This is troublesome in that it causes an undue settling and separation of the heavier components of the coating. Because the product of the present invention has characteristics similar to partial thermally polymerized oils as Well as oils which have been polymerized with oxygen, it is more readily compatible with such products as certain synthetic resins.

A further distinction in the present invention is in its application to the semi-drying oils such as soya bean oil. Normally this oil and its polymerization products are slow in drying, hence its use in normal products is greatly restricted. The soya' bean oil polymerization product resulting from our process assumes a much faster drying rate approximating that of linseed oil, thereby greatly widening the use of this oil in paints and other similar coatings.

In the present invention we have found that when unsaturated fatty oils have been partially blown with air or an oxygen containing gas at temperatures not exceeding substantially 300 F., oxygen is added to the molecules of the oil at the double bonds in the form of oxy, peroxy When oils thus prepared are further treated by the addition of a relatively small amount of an acid of the class which dissociates into hydrogen ions, there is a rapid increase in viscosity as well as mineral spirit tolerance without substantial increase in color or other undesirable characteristics. The change is occasioned by the fact that molecules are linked one to another at the points where the oxygen addition products exist, thereby liberating the catalyst so that the latter does not remain in the final product. An important feature of the present invention is that polymerization occurs at relatively low temperatures, thus avoiding the formation of harmful residues.

The active catalyst which we have found to be mostsuitable is sulfuric acid, this material is relatively inexpensive and readily dissociates hydrogen ions.

Our concept of the most desirable method of conducting the process is to first partially oxidize the oilatthe double bonds such as by blowing with air at temperatures ranging between 300 F. until the iodine value is substantially reduced. In the case of refined linseed oil, the iodine value is reduced 20100 units, and in the case of refined soya bean oil the iodine value is reduced 10-60 units. The polymerization is effected by adding the acid in relatively small catalytic amounts, in the range of 0.2% to 0.5% of the weight of the oil, in dilute form.-

It is essential that the temperature should not exceed the range of substantially 70160 F. and in no instance beyond 200 F., for if the temperature is permitted to rise beyond that limit other reactions will occur, including The mixture of blown oil and acid catalyst is agitated in any well known manner until the desired viscosity is obtained, whereafter the reaction is terminated by the addition of a sufi'lcient amount of a neutralizing agent to partially neutralize the free acid present in the mixture. Although substantially any form of alkali may be used, to avoid the cloudiness caused by water solutions, a non-aqueous alkali such as triethanolamine is preferred. The actual amount of neutralizing agent may be less than the stoichiometrical amount as it is only necessary to partially neutralize the free acid.

In carrying out the polymerization it is desirable that some mineral spirits be previously added to the blown oil as this materially reduces the viscosity of the oil and permits the reaction to occur with greater ease and avoids 9 4 structures of the oxy groups and the polymer are not LINSEED necessarily as represented.

Blown Acid Acid Base Oil Treated Treated H H o11@100% 011 @70% 5 Solids Solids R--C=CR O: RC|1-(]3-R' H2804 O-0 Acid Number 5.0 8.0 5. 6 l it' 5 5g i 1% iscos 0 es t. 5 I? I? H' M/S TOi QIEHOB (Volume) 4-1 12-1 -1 R(IJ CRR-(!J-(IER R+-(IJ R' 1e 0 $11 HO 0 o 0 zmsoi- *SOYA H S 04 H S 04 i (I) 0 Acid Number 6, 8 13.0 9.1 Color 6 10 9-10 Viscosity (poises) 25 575 17. 6 H H M/S Tolerance (Volume) 8-1 32-1 23-1 (Sometimes infinite miscibility with M/S) 2 12 R and R are extenslons of the fatty acid mole' The final product consists of a polymer which is light After neutralizin the final rod t t d t in color, and its undiluted form has a viscosity in excess a tem erature of $3 1 F F d i i of 500 poises, which is readily miscible in mineral spirits. sixteeg hour to our; th 5: P6310 e g The product is free of all traces of the catalyst, is quick S 6 pr 1 c am a s a e drying and will not substantially penetrate into the surface viscosity by assuring a complete neutralization of the free 1 acid used i bod in the H to which it has been applied.

11 y g o In the past it has been the practice to use as a vehicle for the olymerized oil, mineral spirits which contain E m l 1 p xa e aromatic components. These components 211d materially Linseed oil was blown with air at a temperature of 3 the i f p g f ofhthe f g f a 280 F until the iodine value was reduced to 130 The ey are 0 Jecuona m t ey 1g y lrrita a 4- to the olfactory nerves and are, thererore, not desirable own oil was admixed with mineral spirit and the 30 i a when used in connection with coatings intended for inmixture agitated and maintained at 140 1. while 0.4%

terior use. There is currently a large demand for paint H 80 in dilute form (1-1) was added in four incre- 1.

oils and vehicles which can be used witn odorless solvents ments. When the viscosity had reached the desired numbe]: th reaction was neutralized and the roduct cured for interior paints and varnish to avoid the ob ectionable b a s maintained at 120 F for hours Test and irritating odors of present type products. While odorg fgouow less mineral spirits are known, they could not be used 5 because of their low solvency characteristics with polymerized products, since the odorless mineral spirits have a limited compatibility with polymerized products heretog is gggg gfg 40 fore commercially available The essential characteristics of these two types of mineral spirits are:

1.25 07 5-1 2.25 7 7-1 3.2 8 8-1 Approx; Kauri 4.8 8 10- 1 V M. S. Boiling Butanol 10.7 8-9 11-1 Range, Val. 15.0 8-9 12-1 F. 33.0 10 12-1 Add .5% Triethanolainiue regular 325-400 34-10 10 12-1 odorless 300-460 24-28 In the instance of regular mineral spirits, as set forth Example 2 above, the product of our invention has a minimum tolerance of about 10 to 1, which is about equal to the best g bean q a temperature of forms of competitive products. When odorless mineral 280 Its lofhne Vfflue f to The spirits of the type set forth heretofore are used, it has blown 3 was admlxfd Wlth 30/0 9? mlneral 891m and been found that they have limited compatibility with PQ Y under F cgndltlons as Example 1 other products, but the product of the present invention using 0.5% sulphuric ac1d in dilute form. The results combines to form a Solution with approximately three the test were: or more parts of the odorless mineral spirit, which makes the product of the present invention highly desirable for use with interior paints and coatings. T1me,mln- C0101 g In summary, our invention demonstrates a new and useful process whereby unsaturated fatty oils are acti- 2 1 H I H vated through treatment with air or oxygen under closely 3 0 6 controlled conditions for subsequent catalytic polymerization to produce products having unusual features. Be- 5.7 6-7 14-1 10,7 7 7 2H cause the product is made at relatively low temperatures, g-g g 3 complex by-products are omitted, wherefore the product 3-1 is compatible with low solvency odorless mineral spirits. ethanolamme M 2m Also, because the final product is to a degree relatively W similar to thermally polymerized oils and also oils which have been blown with air, it is miscible with relatively high proportions of either of these products and can act Typical analyses of linseed andsoy-a bean oil after air to combine several different types of products. blowing, acid treatment, and with 30% mineral spirits The invention is not limited to any particular type of are: fattyoil, since it is believed to be applicable to any form of unsaturated fatty oils, and is therefore limited only to the extent as set forth in the following claims.

We claim: 7

l. A process of treating an unsaturated fatty oil to form polymers which consists of blowing said oil to add oxygen to the unsaturated bond at a temperature between 70 F. and 300 F., forming a mixture of said blown oil and substantially 0.2% to 0.5% sulfuric acid,

maintaining the mixture at a temperature between 70 F. and 160 F. until a substantial portion of the mixture is polymerized and thereafter adding to the mixture a sufficient amount of an alkaline neutralizing agent to partially neutralize the sulfuric acid.

2. A polymer formed of an unsaturated fatty oil blown at a temperature between 70 F. and 300 F. until oxy- 5 acid catalyst is at least partially neutralized.

References (Iited in the file of this patent UNETED STATES PATENTS 2,298,916 Auer Oct. 13, 1942 10 2,383,60'l Keim Aug. 28, 1945 2,717,882 Kiebler et al Sept. 13, 1955 OTHER REFERENCES Bailey: Industrial Oil and Fat Products, 2nd edition,

15 1951, p 902 to 904. 

1. A PROCESS OF TREATING AN UNSATURATED FATTY OIL TO FORM POLYMERS WHICH CONSISTS OF BLOWING SAID OIL TO ADD OXYGEN TO THE UNSATURATED BONDS AT A TEMPERATURE BETWEEN 70*F. AND 300*F., FORMING A MIXTURE OF SAID BLOWN OIL AND SUBSTANTIALLY 0.2% TO 0.5% SULFURIC ACID, MAINTAINING THE MIXTURE AT A TEMPERATURE BETWEEN 70* F. AND 160*F. UNTIL A SUBSTANTIAL PORTION OF THE MIXTURE IS POLYMERIZED AND THEREAFTER ADDING TO THE MIXTURE A SUFFICIENT AMOUNT OF AN ALKALINE NEUTRALIZING AGENT TO PARTIALLY NEUTRALIZE THE SULFURIC ACID.
 2. A POLYMER FORMED OF AN UNSATURATED FATTY OIL BLOWN AT A TEMPERATURE BETWEEN 70*F. AND 300*F. UNTIL OXYGEN HAS BEEN ADDED TO THE UNSATURATED BONDS THEREOF, SAID BLOW MATERIAL THEN TREATED AT A TEMPERATURE BETWEEN ROOM TEMPERATURE AND ABOUT 200*F. WITH A CATALYSTIC AMOUNT OF AN AQUEOUS SULFURIC ACID SOLUTION, AND THEREAFTER THE ACID CATALYST IS AT LEAST PARTIALLY NEUTRALIZED. 